MOLECULAR ENERGY LEVELS

DR IMRANA ASHRAF
OUTLINE

q  MOLECULE
q  MOLECULAR ORBITAL THEORY
q  MOLECULAR TRANSITIONS
q  INTERACTION OF RADIATION WITH MATTER
q  TYPES OF MOLECULAR ENERGY LEVELS
q  MOLECULE

q  In nature there exist 92 different elements that correspond to stable atoms.

q  These atoms can form larger entities- called molecules.
q  The number of atoms in a molecule vary from two - as in N2 - to many
thousand as in DNA, protiens etc.
q  Molecules form when the total energy of the electrons is lower in the
molecule than in individual atoms.
q  The reason comes from the Aufbau principle - to put electrons into the
lowest energy configuration in atoms.
q  The same principle goes for molecules.
q  MOLECULE

q  Properties of molecules depend on:

§  The specific kind of atoms they are composed of.

§  The spatial structure of the molecules - the way in which the atoms
are arranged within the molecule.

§  The binding energy of atoms or atomic groups in the molecule.

TYPES OF MOLECULES

q  MONOATOMIC MOLECULES
§  The elements that do not have tendency to form molecules.
§  Elements which are stable single atom molecules are the noble gases : helium,
neon, argon, krypton, xenon and radon.
q  DIATOMIC MOLECULES
§  Diatomic molecules are composed of only two atoms - of the same or different
elements.
§  Examples: hydrogen (H2), oxygen (O2), carbon monoxide (CO), nitric oxide (NO)
q  POLYATOMIC MOLECULES
§  Polyatomic molecules consist of a stable system comprising three or more
atoms.
TYPES OF MOLECULES
q  Empirical, Molecular And Structural
Formulas
q  Empirical formula: Indicates the simplest whole number ratio of all the
atoms in a molecule.
The empirical formula of glucose is CH2O.
q  Molecular formula: Describes the exact number and type of atoms in a
single molecule of a compound.
The molecular formula for glucose is C6H12O6
q Structural formula: Indicates not only the number of atoms
but also their arrangement in space.
Formulas
Difference between Isomers and Allotrope
ISOTOPE
Atoms with the same number of protons but different number of neutrons are
called isotopes. By changing the number of neutrons, isotopes still maintain the
same overall neutrality and hence the chemical behavior remains unchanged.
ISOMERS
Isomers are two molecules with the same atoms joined together in a different
shape. They have same molecular formula but different chemical structure. For
example : Butane and isobutane
ALLOTROPE
They are different structural forms of the same element but can exhibit quite
different physical and chemical properties. For example, carbon, diamond,
graphite…
Examples of isomers and allotrope

Structural Isomers:
same molecular formula
but different structural
formula

Allotropes of carbon:
Diamond and graphite are
two allotropes of carbon:
pure forms of the same element
that differ in structure.
Molecular Spectroscopy

Molecular spectroscopy : is the study of the interaction of

electromagnetic (EM) radiation with matter.
q  Based on the analysis of EM radiation that is emitted, absorbed, or
scattered by molecules- we can have information on
q  Chemical analysis
q  Molecular structure (bond lengths, angles, strengths, energy
levels, etc...)
Energy Levels

•  A quantum mechanical system or particle that is bound—that is, confined

spatially —can only take on certain discrete values of energy- called
energy levels.

•  The term is commonly used for the energy levels of electrons in atoms,
ions or molecules- which are bound by the electric field of the nucleus.

•  Can also refer to energy levels of nuclei or vibrational or rotational energy

levels in molecules.
Ground and excited states

•  If an atom, ion, or molecule is at the lowest possible energy level,

it and its electrons are said to be in the ground state.

•  If it is at a higher energy level, it is said to be excited, or any

electrons that have higher energy than the ground state are
excited.

•  If more than one quantum mechanical state is at the same energy,

the energy levels are called degenerate energy levels.
Chemical Bonds

•  Chemical bonds between atoms in a molecule form because they make the
situation more stable for the involved atoms.
•  Covalent bond:, involves the sharing of electron pairs between atom.
•  As atoms approach each other to covalently bond -their orbitals affect each
other's energy levels to form bonding and anti-bonding molecular orbitals.
•  The energy level of the bonding orbitals is lower, and the energy level of the
anti-bonding orbitals is higher.
•  For the bond in the molecule to be stable - the covalent bonding electrons
occupy the lower energy bonding orbital - which may be signified by such
symbols as σ or π.
q  Molecular Orbital Theory

q  Orbitals of individual atoms interact to produce new orbitals - called

molecular orbitals
N
Φ = ∑ aiϕ i
i =1

Φ is the molecular orbital, φ is an atomic orbital and a is a coefficient

Molecules have discrete energy levels - no continuum between levels.
Absorbs electromagnetic radiation when the energy of photon corresponds
to the difference in energy between two states.
q  Molecular Energy Levles

Energy can be stored either as potential energy or kinetic energy, in a

variety of ways including

•  Translational energy: small amounts of energy stored as kinetic energy.

•  Rotational energy: kinetic energy associated with the rotational motion
of molecules.
•  Vibrational energy: the oscillatory motion of atoms or groups of atoms
within a molecule (potential energy ↔ kinetic energy exchange).
•  Electronic energy: energy stored as potential energy in excited
electronic configurations.
All except the Translational energy are quantized
Emolecule = Erotational + Evibrational + Eelectronic
q  Molecular Transitions

tomic and molecular vibrations correspond to excited energy levels in quantum mechanics
Excited level

⇔
Energy
ΔE = hν

Ground level

The atom is vibrating at frequency, ν. The atom is at least partially in an excited state.

q  For a given frequency only one value of quantum energy for the photon is possible
q  Transitions between energy levels occur by absorption, emission and stimulated
emission of photons
 q  Spontaneous Emission

q  When an atom/ molecule in an excited state falls to a lower energy level - it emits a
photon

Excited level
Energy

Ground level
q  Molecules typically remain excited for a few nanoseconds- upon de-excitation emit a
photon of light.
q  This process is called fluorescence .
Stimulated Absorption

q  Atoms and molecules can also absorb photons, making a transition from a lower
level to a more excited one
q  Stimulated Emission

In 1916, Einstein showed

another process called stimula
emission can also occur
q  Molecular Trnasitions

Before After

Spontaneous
emission

Absorption

Stimulated
emission
 Electromagnetic (EM) radiation consists of photons (elementary particles) which behave
as both particles and waves.

The image to the right shows the wave-like character associated with a single photon of EM
radiation.
Electromagnetic radiation
In the x,z plane there is an oscillating electric field (E)
In the y,z plane there is an oscillating magnetic field (B)

Both are in phase but perpendicular to each other.

q  Electromagnetic (EM) radiation consists of photons which
behave
Key as both particles and waves.
equations

c = speed of light (2.998x108 ms-1)

c = speed
λ = wavelength (m) of light (2.998x108 ms-1)
λ = wavelength
ν = frequency (s-1) (m)
= wavenumber (m-1)
ν = frequency (s-1)
= wavenumber (m-1)
 Electromagnetic spectrum
ectromagnetic spectrum
q  INTERACTION OF RADIATION WITH MATTER

here are no available

ntized energy levels
ching to the quantum
rgy of the incident
iation, then the
terial will be
nsparent to that
ation

Wavelength
q  X-RAY INTERACTIONS

Quantum energies of x-ray photons are too high to be

bsorbed by electronic transitions in most atoms -
nly possibility is complete removal of an electron
rom an atom - x-rays are ionizing radiation

Photoionization: If all the energy is given to an electron

Compton scattering: If part of the energy is given to an
electron and the rest to a lower energy photon
  UlTRAVIOLET INTERACTIONS

Near UV radiation is absorbed very strongly

n the surface layer of the skin by electron
transitions
At higher energies, ionization limit for many
molecules are reached and the more
dangerous photoionization processes occur.
Sunburn is primarily an effect of UV
radiation, and ionization produces the risk
of skin cancer
q  VISIBLE LIGHT INTERACTIONS

q  Visible light is also absorbed by electron transitions

q  Higher energies are absorbed more relative to low energies - red light is less
strongly absorbed than blue light
q  Absorption of visible light causes heating, but not ionization
q  Car windshields transmit visible light but absorb higher UV frequencies
q  INFRARED (IR) INTERACTIONS

he energy level of infrared light

orresponds to the energy
equired to cause molecular
ibrations
ibrations arise as molecular
onds are not rigid but behave
ke springs
 q  INFRARED (IR) INTERACTIONS _ CONT’D
Vibrational transitions are Sub-divided into two classes:
Stretching : symmetric and asymmetric
Bending: scissoring, rocking, wagging and twisting
Stretching frequencies are higher than corresponding bending frequencies - it i
easier to bend a bond than to stretch or compress it
Bonds to hydrogen have higher stretching frequencies than those to heavier
toms.
Triple bonds have higher stretching frequencies than corresponding double bon
which in turn have higher frequencies than single bonds
q  MICROWAVE INTERACTIONS

Quantum energy of microwave photons ( 10-5-10-3 eV) matches the ranges of energies
separating quantum states of molecular rotations.
Like electronic and vibrational transitions rotational motion of molecules is quantized
Absorption of microwave radiation causes heating due to increased molecular rotational
activity
Most matter transparent to µ-waves, microwave ovens use high intensity µ-waves to heat
material
q  MOLECULAR ENERGY LEVELS
q  MOLECULAR ENERGY LEVELS _ CONT’D

Radiation can be absorbed

or emitted if the molecule
changes any of its energy
states.
 q  MOLECULAR ENERGY LEVELS _ CONT’D

he relative energy of the spacings between energy levels for various types of
ansitions in a molecule are in the order:

Rotational Vibrational Electronic

Transition << Transition << Transition

1-20 cm-1 2000-4000 cm-1 10000-50000 cm-1

The various types of energy transitions occur in different regions of the EM-
spectrum and do not overlap
q  MOLECULAR ENERGY LEVELS _ CONT’D

Vibrational
Transition

2000-4000 cm-1

Infrared

Rotational Electronic
Transition Transition

1-20 cm-1 10000-50000 cm-1

Microwave UV-Visible
 q  ABSORPTION SPECTRA OF MOLECULES _
CONT’D

q  Electronic, vibrational and rotational

energy levels are superimposed
q  The absorption spectrum of a
molecule is determined by all
allowed transitions between pairs of
energy levels that interact with the
radiation field
V = Vibrational quantum number

J = Rotational quantum number

VIBRATIONAL MOLECULAR LEVELS

q  Like atoms - molecular motion is governed by quantum mechanics.

q  Chemical bond acts like a spring and can display Simple harmonic
motion
q  Energies due to vibration are quantized : Eν = ħω (ν + ½)
q  Vibrational quantum number v = 0,1,2,3,…
q  Angular frequency ω = √k⁄meff
q  An effective spring constant k for the bond involved
q  Effective mass meff
VIBRATIONAL MOLECULAR LEVELS _ CONT’D

q  ½ℏω comes from quantum mechanics and represents zero-point energy

q  The zero point energy ½ ω implies molecule never stops vibrating - even
when its in the v = 0 state
q  Zero point energy cannot be harvested or extracted - Still exists at
absolute zero - All molecules are then in v = 0 state
q  Energy levels are equally spaced with separation ω
q  Obey selection rule ∆v = ±1
VIBRATIONAL MOLECULAR LEVELS _ CONT’D

q  For diatomic molecule with mass M1 and M2 - the effective mass

meff = (M1M2)⁄(M1 + M2)
q  Energy scale for molecular vibrations is much less than that for
electronic excitations
q  Excitation energies correspond to IR region of the spectrum
q  Vibrational levels are built on electronic states – each electronic
state will host the whole range of vibrational states
Vibrational excitation and de-excitation
q  VIBRATIONAL MOLECULAR LEVELS _ CONT’D

Fundamental or normal modes

ν1 Symmetric stretch
ν2 Bend (Scissoring)
ν3 Asymmetric stretch
normal mode is IR-active if the dipole moment
anges during mode motion.
vertones, combinations and differences of
ndamental vibrations are also possible (e.g., 2v1,
+v3 etc.)
non-linear molecule of N atoms has 3N-6 normal
odes of vibration; a linear molecule has 3N-5.
q  ROTATIONAL MOLECULAR LEVELS

q  In quantum mechanics - the rigid rotor has energy levels

EJ = ħ2 ⁄ 2ℑ J(J +1)

q  ℑ is the moment of inertia

q  J is the angular momentum: J = 0,1,2,3,…

q  The quantity ħ2 ⁄ 2ℑ is called the rotational parameter

q  Moment of inertia - hence rotational parameter - can be different for

each rotation axis
q  ROTATIONAL MOLECULAR LEVELS _ CONT’D

q  Excitation energies correspond to the microwave region

q  Energy scale for rotations << vibrations

q  Each vibrational level has rotational bands built on it

q  Selection rule ∆J = ±1
ROTATIONAL LEVELS
q  VIBRATIONAL-ROTATIONAL TRANSITION

q  Relative positions of transitions

in the absorption spectrum of a
molecule
q  P branch (ΔJ = -1)
q  Q branch (ΔJ = 0)
(pure vibration)
q  R branch (ΔJ = +1)
 Electronic levels

q  In molecules we have two opposing forces - the repelling force of the

nuclei, and the binding force of the electrons.

q  If the orbit of the electrons change then the binding force will change,
i.e. the net potential energy of the molecule will change.

q  This means that the inter-atomic distance will change

q  Different electronic levels will have different rotational and vibrational

constants
ENERGY LEVELS

q  Taking rotations, vibrations, and electronic excitation into account

En,v,J = En + Ev + EJ
q  Complex molecules may have many vibrational modes, rotational
modes, etc
q  The combination of these different modes leads to a “smearing” of the
discrete spectrum - so that broad bumps appear rather than discrete
lines
 Simple versus Complex molecules

electronic
vibrational
otational
otal energy E V R T

E V R T
E V R T
ENERGY LEVELS _CONT’D

q  Ignoring electronic excitation _ the total internal energy of a molecule i

the sum of its vibrational and rotational energy.
Ev,J = ħω (v + ½) + ħ2 ⁄ 2ℑ J(J +1)
q  The wave-number of a spectral line is given by the difference of the term
values of the two states
q  A change in vibrational quantum number v is accompanied by a change i
rotational quantum number J - according to the selection rule ΔJ = 0, ±1
ENERGY LEVELS _CONT’D

q  The complete set of rotational transitions between two vibrational levels

is known as a ‘band’

q  A band normally consists of three separate sequences; If

•  ΔJ=0 we have the Q branch

•  ΔJ=1 the R branch

•  ΔJ=-1 the P branch

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